Esters of p-di(omega-hydroxyalkoxy)benzenes



1 Patented Dec. 14, 1948 ESTERS OF P-DI(OMEGA-HYD ROXY- ALKOXY)BENZENES Edward 0. Ramler, North Arlington, N. .L, as-' slgnor to E. I. du Pont de Nemours & Company, Wilmington, DcL, a corporation of Delaware No Drawing. Application May 29, 1946,

' Serial No. $73,156-

This invention relates to the preparation of new polymerizable compounds, the formation of polymers therefrom and, more particularly, to the formation of new hard, clear resins of low water 790 parts of absolute ethanol were placed in a 4 Claims. (Cl. 260-83)- 2 three-necked flask equipped with a stirrer, calcium chloride drying tube, and reflux condenser. 220 parts of hydroquinone were added and dissolved in the ethanol. 96 parts (4 mols') of soabsorption. 5 dium were then added to the solution in small Heretofore there has not been available a satslices and the reaction mixture was allowed to isfactory bi-functional monomer which-will autostand for a period and then refluxed for one polymerize or copolymerize with other polymerhour. At the end of the hour, 354 parts of ethizable compounds to yield a low water absorptive ylene chlorohydrin were added dropwise to the resin of high transparency and improved scratch mixture without stirring and the mixture was I resistance. then refluxed with stirring for a short time. An object of the present invention is to pre- Thereupon the mixture was filtered while hot to pare new polymerizable compounds and polymers remove the sodium chloride formed and the filand copolymers therefrom. A further object is trate, upon cooling, threw down a'heavy precipito prepare new iii-functional compounds which tate which was filtered off. The precipitate was will yield polymers and copolymers of extremely recrystallized from absolute methanol, yielding low water absorptive characteristics andexcelp-di(beta-hydroxyethoxy)benzene. This coin lent transparency and hardness and scratch repound was further purified by standard procedure. sistance. Other objects will be apparent from 150 parts of the p-di(beta-hydroxyethoxy)benthe description of the invention given hereinafter. zene,- 133 parts of methacrylic acid, 5 parts of 113 The above objects are accomplished according droquinone, 5 parts of a powdered decolorizing to the present invention by esteriiying both hydcarbon, and 6 parts of a powdered diatomaceous roxy groups of p-di(omega-hydroxyalkoxy)bensilica as an inert .filter aid, were put into 44C zenes with an acid from the group consisting of parts of benzene mixed with 9.17 parts of concenacrylic and alkacryllc acids and substituted acrytrated sulfuric acid. This mixture was introlie and alkacrylic acids, and polymerizing the reduced into a three-necked flask equipped with a sulting esters either alone or in admixture with thermometer, cooling condenser and water reother polymerizable compounds. ceiver, and heated until approximately 80% of It has been found these esters of p-di(omegathe theoretical water resulting from the esterifl- .hydloxyalkoxymenzenes are readily p y cation reaction was collected. The remaining reable, either alone or with other polymerizable action mixture was then filtered hot to remove compounds, to give hard, transparent resins of I the decolorizing carbon and powdered diatomaexceptionally lovs water absorption. The p-di(oceous silica. and the filtrate was allowed to stand mega-methacryloxyalkoxy)benzenes and, specifiover a two-day period at the end of which time 0 3. p- -m th ry y h xylbenzene, are a small amount of a crystalline product appeared especially preferred as yielding polymers and 00- on the bottom of the flask. The filtrate was then polymers of outstanding properties. Monomeric shaken with 10% sodium hydroxide and a large p-di( eta-me hacl'y xy y)benzene is bebatch of crystals appeared. These crystals were lleved to have the formula: filtered and dried, subsequently recrystallized in 0 40 absolute ethanoLwashed with water and again l dried. The product obtained, p-di(betametha- 'QO' 'E' cryloxyethoxy) benzene was in the form of white, (SH; H1 odorless, flaky crystals melting'at about 79 C. and is readily prepared by, reacting methacrylic acid with p-di(beta-hydroxyet.hoxy) benzene Example H which has the formula 100 parts of p-di(beta-methacryloxyethqiiy) benzene, as made in Example I, and 0.2 part; oinocmcmoOocnicmoH benzoyle peroxide were mixed ma. beaker and, heated at 100 C. In ten minutes the material The following examples wherein the proporhad polymerized to yield a hard, clear resin of tions are by weight unless otherwise specified, low water absorption. illustrate specific embodiments of this invention: Emmple HI Example I 20 parts of p-di(beta-methacryloxyethoxy)- benzene, as made in Example I, parts of a be substituted for the 7 monomeric methyl methacrylate, and 02 part of benzoyl peroxide were mixed together and the mixture'was heated at 75 C. for 72 hours during which time it polymerized to a hard, transparent resin having a Rockwell hardness equal to 104 on the Mscale and a yield temperature 129 C.

The yield temperature" above referred to is determined by immersing a molded specimen of the resin of the size 2.5 x 0.5 x 0.05 inches approximately one inch below the surface of a mineral oil bath (such as a heavy paraffin oil) and establishing the temperature at which the test piece sags 0.06 inch under a load of 27.5 grams applied with a two inch moment against the smallest dimension of the test piece.

E's-ample IV 7.5 parts of p-di(beta-methacryloxyethoxy)- I benzene, as made in Example I, and 7.5 parts of tetraethylene glycol dimethacrylate were mixed together and heated to 70 C. to yield a clear solution. To this solution was added 0.015 part of benzoyl peroxide which dissolved readily therein and the solution was then polymerized at a temperature of 70 C. in seven minutes to a hard, clear resin having a Rockwell hardness equal to 111 on the R scale and a water absorption of 1.17%. The water absorption of straight polymerized tetraethylene glycol dimethacrylate was 2.0%. The copolymer of this example, while actually not testing as hard as straight polymerized tetraethylene' glycol dimethacrylate on the Rockwell scale, nevertheless exhibits considerably improved scratch resistance as compared to straight polymerized tetraethylene .glycol dimethacrylate.

It will be understood that the above examples are merely illustrative and the present invention broadly comprises reacting p-di(omega-hydroxyalkoxy benzenes with acrylic or alkacrylic acids or substitute acids to form esters and polymerizing the esters either alone or with other polymerizable compounds.

While the esters obtained by reacting p-di- (beta-hydroxyethoxy)benzene with acrylic or alkacrylic acids are preferred in that they yield polymers of exceptional properties, the esters obtained by using other p-di(omega-hydroxyalkoxy)benzenes, such as p-di(omega-hydroxypropoxy)benzene and p-di(omega-hydroxybutoxy) benzene, readily prepared according to the rocedure set forth in Example I, in place of p-di- (beta-hydroxyethoxy) benzene are also easily polymerized to give resins characterized by low water absorption and valuable as a component of copolymers having excellent scratch resi tance. Other alkacry'lic acids, as well as acrylic aciil, may methacrylic acid in the processor Example I to yield the corresponding esters which are likewise polymerizable to low water absorptive resins. Such acids include acrylic acid, chloroacrylic acid, and other halide substituted acrylic and allacrylic acids, ethacrylic acid and crotonic acid. v

A particular advantage of these compounds is that they readily polymerize with other polymerizable compounds to give resins of high quality and notably low water absorption. These copolymers are, in general, harder than the straight polymer of the other component of the copolymer although in some instances this is not true on the basis of Rockwell hardness measurements.

However, the particular property usually sought in resins of this type is scratch resistance and, in that property, the herein described compounds give copolymers of appreciable improvement over the straight polymer of the other component of the copolymer.

The benzene compounds of this invention may be copolymerized to advantage with other polymerizable compounds generally. Polymerizable vinyl compounds such as vinyl acetate, vinyl butyrate, and other vinyl esters, vinyl chloride and other vinyl halides, vinyl cyanide, and styrene, alkyl esters of acrylic acid such as methyl, ethyl, and butyl acrylates, and alkyl esters of alkacrylic acids including methacrylic and ethacrylic acid esters such as the methyl, ethyl, butyl, isobutyl, secondary butyl, and tertiary amyl esters, are all adapted to be copolymerized with these benzene compounds to give resins of low water absorption. Moreover, the acrylic and methacrylic acid esters, of such polyhydric alcohols as disclosed in copending application Serial No. 671,393, filed May 21, 1946 in the names of A. W. Anderson and E. 0. Ramler, where interpolymerized with the benzene compounds of this invention, as in Example IV, yield particularly useful compositions. The proportion of each component of the copolymer may be varied widely as will be appreciated by those skilled in the art.

a Members of the class of p-di(omega-hydroxyalkoxylbenzenes have been synthesized heretofore, but the herein disclosed esters of these compounds are new. As disclosed, these biiunctional polymerizable esters are readily formed by reacting specific p-di(omegmhydroxyalkoxy) benzenes with the desired acid, i. e., acrylic, methacrylic, ethacrylic acids, and the like.

Thus it will be seen an outstanding advantage of the present invention is that it provides a new class of readily prepared polymerizable compounds highly useful as components of copolymers characterized by two greatly desired properties, namely, scratch resistance and low water absorption. These benzene compounds also form useful polymers when polymerized in the absence of other polymerizable compounds.

As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. As new compounds, p-diibeta-hydroxyethoxy)benzenes in which both hydroxy groups are esterified with an acid from the group consisting of acrylic acid, chloroacrylic, methacrylic, ethacrylic, and crotonic aci 2. As a new compound, p-di(beta-methacryloxyethoxy) benzene.

3. A resin comprising a polymer of a p-di(betahydroxyethoxylbenzene in which both hydroxy groups are esterified with an acid from the group consisting of acrylic acid, chloroacrylic, methacrylic, ethacrylic, and crotonic acids.

4. A resin comprisinga polymer of p-di(betamethacryloxyethoxy) benzene.

EDWARD o. RALIILER. REFERENCES orrsn The following references are of record in the.

Name Date Coleman Jan. 4, 1944 Number 

